TYPE Review
PUBLISHED 21 November 2023
OPEN ACCESS
EDITED BY
Mathieu Roskosz,
Muséum National d’Histoire Naturelle,
France
REVIEWED BY
Sung Keun Lee,
Seoul National University, Republic of
Korea
Sami Mikhail,
University of St Andrews, United Kingdom
*CORRESPONDENCE
Terry-Ann Suer,
tsuer@lle.rochester.edu
RECEIVED 05 February 2023
ACCEPTED 02 November 2023
PUBLISHED 21 November 2023
CITATION
Suer T-A, Jackson C, Grewal DS, Dalou C
and Lichtenberg T (2023), The
distribution of volatile elements during
rocky planet formation.
Front. Earth Sci. 11:1159412.
doi: 10.3389/feart.2023.1159412
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© 2023 Suer, Jackson, Grewal, Dalou and
Lichtenberg. This is an open-access
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Frontiers in Earth Science
DOI 10.3389/feart.2023.1159412
The distribution of volatile
elements during rocky planet
formation
Terry-Ann Suer 1,2*, Colin Jackson 3, Damanveer S. Grewal 4,
Celia Dalou 5 and Tim Lichtenberg 6
1
Laboratory for Laser Energetics, University of Rochester, Rochester, NY, United States, 2Steward
Observatory, University of Arizona, Tucson, AZ, United States, 3Earth and Environmental Sciences, Tulane
University, New Orleans, LA, United States, 4Division of Geological and Planetary Sciences, California
Institute of Technology, Pasadena, CA, United States, 5Université de Lorraine, CNRS, Centre de
Recherches Pétrographiques et Géochimiques, Nancy, France, 6Kapteyn Astronomical Institute,
University of Groningen, Groningen, Netherlands
Core segregation and atmosphere formation are two of the major processes that
redistribute the volatile elements—hydrogen (H), carbon (C), nitrogen (N), and sulfur
(S)—in and around rocky planets during their formation. The volatile elements by
definition accumulate in gaseous reservoirs and form atmospheres. However, under
conditions of early planet formation, these elements can also behave as siderophiles
(i.e., iron-loving) and become concentrated in core-forming metals. Current
models of core formation suggest that metal-silicate reactions occurred over a
wide pressure, temperature, and compositional space to ultimately impose the
chemistries of the cores and silicate portions of rocky planets. Additionally, the
solubilities of volatile elements in magmas determine their transfer between the
planetary interiors and atmospheres, which has recently come into sharper focus in
the context of highly irradiated, potentially molten exoplanets. Recently, there has
been a significant push to experimentally investigate the metal-silicate and magma-
gas exchange coefficients for volatile elements over a wide range of conditions
relevant to rocky planet formation. Qualitatively, results from the metal-silicate
partitioning studies suggest that cores of rocky planets could be major reservoirs of
the volatile elements though significant amounts will remain in mantles. Results
from solubility studies imply that under oxidizing conditions, most H and S are
sequestered in the magma ocean, while most N is outgassed to the atmosphere,
and C is nearly equally distributed between the atmosphere and the interior. Under
reducing conditions, nearly all N dissolves in the magma ocean, the atmosphere
becomes the dominant C reservoir, while H becomes more equally distributed
between the interior and the atmosphere, and S remains dominantly in the interior.
These chemical trends bear numerous implications for the chemical differentiation
of rocky planets and the formation and longevity of secondary atmospheres in the
early Solar System and exoplanetary systems. Further experimental and modeling
efforts are required to understand the potential of chemical and physical
disequilibria during core formation and magma ocean crystallization and to
constrain the distributions of volatile elements in the interiors and atmospheres
of rocky planets through their formation and long-term geologic evolution.
KEYWORDS
planet formation, metal-silicate partitioning, magma-atmosphere exchange, core-
mantle differentiation, volatile elements, atmosphere formation, super-earth exoplanets
01 frontiersin.org
Suer et al.
1 Introduction
Hydrogen, carbon, nitrogen, and sulfur are abundant volatiles in
the atmospheres of terrestrial planets in the Solar System and are
expected to similarly dominate the gaseous envelopes of extrasolar
rocky planets (Wordsworth and Kreidberg, 2022). Depending on the
prevailing thermodynamic and compositional properties, these
elements can be present in atmospheres in oxidized (e.g., H2O,
SO2, CO2) or reduced forms (e.g., H2, H2S, CO) (Gaillard, et al.,
2022). A significant proportion of a planet’s volatile elements can be
locked up in deep reservoirs such as cores and mantles whose bulk
compositions are largely determined during early planet formation
(Rubie, et al., 2007). Atmospheric outgassing (magma-gas exchange)
can occur simultaneously with core-mantle differentiation while
planets are hot enough to sustain magma oceans (Elkins-Tanton,
2012; Hirschmann, 2012). Prior to the outgassing of their secondary
atmospheres, large rocky planets (>0.2 ME) that formed early likely
accreted primary H and/or He nebular atmospheres that would have
interacted with their early magma oceans (Sasaki, 1990; Zahnle,
et al., 2010). Although Earth lost its primordial atmosphere (Catling,
et al., 2001), studies of exoplanetary systems have revealed that some
rocky planets can retain such envelopes throughout their evolution
(Misener and Schlichting, 2021). Atmospheres can also be strongly
modified by impact-induced shock heating and erosion (Matsui and
Abe, 1986; Zahnle, et al., 1988; Davies, et al., 2020; Zahnle, et al.,
2020). However, from a geoscientific perspective, the two main
volatile redistribution mechanisms are core formation and magma
outgassing, which we discuss here with particular emphasis on
recent measurements. Volatiles retained within rocky planets’
mantles can reside as various mineral or fluid components and
participate in geological and biochemical processes (Dasgupta and
Hirschmann, 2010; Li, et al., 2013; Mikhail and Sverjensky, 2014;
Armstrong, et al., 2015; Hirschmann, 2018). Significant amounts of
volatile elements, along with other light elements (e.g., O and Si), are
also inferred to be present in the cores of Earth and other rocky
planets such a Mars, where they lower the melting temperature and
density of iron, leading to partially to fully molten cores capable of
sustaining a dynamo (Badro, et al., 2014; Nimmo and Schubert,
2015; Brennan, et al., 2020; Lv and Liu, 2022).
The Earth’s core and mantle inherited their elemental
abundances during Earth’s differentiation. Core-mantle
segregation involved chemical reactions between Fe and silicates
in a reduced (Fe-alloy saturated) magma ocean (Wade and Wood,
2005; Wood, et al., 2006). Geochemical evidence—the abundance of
refractory siderophile elements such as Ni, Co, W and Mo in mantle
peridotite—coupled with metal-silicate partitioning experiments
have led to inferences about the average conditions of core
formation (Ringwood, 1977). The earliest framework for
understanding core-mantle differentiation was provided by
single-stage models in which metals accumulated at the bottom
of the magma ocean before descending into the core (Stevenson,
1981; Stevenson, 1988; Karato and Murthy, 1997; Solomatov, 2007).
These models assumed that the entire core and magma ocean
equilibrated at a common pressure-temperature-oxygen fugacity
and composition (P-T-f O2-X) (Jones and Drake, 1986) and led
to valuable insights on how redox state and planetary size affect core
and mantle chemistry (Righter and Drake, 1996; Wade and Wood,
2005; Corgne, et al., 2009). Early experimental studies of elemental
Frontiers in Earth Science
10.3389/feart.2023.1159412
partitioning during core-mantle-differentiation indicated that the
mantle’s refractory siderophile abundances require metal-silicate
partitioning at pressures from 25 to 30 GPa, equivalent to a magma
ocean depth of 800 km (Li and Agee, 2001). However, later
experiments found that average conditions of 45–55 GPa
(~1,500 km depth) and ≥3500 K (Bouhifd and Jephcoat, 2011;
Siebert, et al., 2012; Fischer, et al., 2015) could better explain the
mantle’s Ni and Co abundances. Large impacts may have provided
the energy for such deep magma oceans and their associated
episodes of core formation (Tonks and Melosh, 1993; Davies,
et al., 2020), although rapid pebble accretion (Johansen, et al.,
2021) could also have led to high temperatures and mantle melting.
Recent experimental studies done on different groups of
elements including highly siderophiles and volatiles have
indicated that one set of P-T-f O2-X condition cannot account for
all the relevant geochemical observables such as the bulk silicate
Earth (BSE) contents in highly siderophile and volatile elements.
More integrated approaches have been developed which consider
the dispersal of impacting materials and degree of chemical
equilibration before segregating into a core and a mantle (Rubie,
et al., 2003; Rubie, et al., 2007; Deguen, et al., 2014). These multi-
stage approaches can account for some geochemical observables
such as the moderately siderophile elemental abundances in the
mantles of smaller planetary bodies, which required metal-silicate
reactions at lower pressure-temperature conditions (Righter and
Drake, 1997; Steenstra, et al., 2016). Though core formation in
terrestrial planets is generally thought to occur at pressures and
temperatures where metal and silicate phases are largely immiscible,
other large-scale processes such as the segregation of a sulfide matte
may accompany or follow core segregation (Rubie, et al., 2016;
Steenstra, et al., 2020). Additionally, density estimates for rocky
exoplanets (Otegi, et al., 2020) and the bulk chemical abundances of
disintegrated planetesimals in the atmospheres of polluted white
dwarfs (Bonsor, et al., 2020; Bonsor, et al., 2022) indicate that the
process of planetary differentiation could be common in planetary
systems.
The failure of single-stage homogenous models to find a unique
P-T-f O2-X condition that can explain all geochemical observables
suggests not only that Earth formed in stages and experienced
disequilibria, but also that accreting material might have changed
over time (Wade, et al., 2012). Indeed, N-body simulations of
planetary accretion (Chambers and Wetherill, 1998; O’Brien,
et al., 2014) imply that fully formed rocky bodies experience
many large impacts during their growth and that radial mixing
of inner and outer Solar System materials occurs concomitantly.
This heterogeneous framework allows for many episodes of core
formation to occur at varying pressures, temperatures, and
compositions (Rubie, et al., 2003; Albarede, 2009; Schönbächler,
et al., 2010). Crucially, heterogeneous models driven by the mass
delivery scenarios of N-body simulations tend to favor the delivery
of more volatile-rich materials, ultimately sourced from the outer
Solar System, later in the accretion process when the potential for
extreme P-T metal-silicate reactions is at its maximum (Halliday,
2013; O’Brien, et al., 2014; Rubie, et al., 2016). However, analyses of
small rocky bodies and coupled to astrophysical and geochemical
models suggest that volatile elements were present in the inner Solar
System well before the later stages of planetary formation (Bar-Nun
and Owen, 1998; Busemann, et al., 2006; Marty, 2012; Halliday,
02 frontiersin.org
Suer et al. 10.3389/feart.2023.1159412

2013; Alexander, 2017; McCubbin and Barnes, 2019; Grewal, et al., rocky planets in these exoplanetary systems (Lichtenberg, et al.,
2021c; Deligny, et al., 2021; Grewal, 2022; Grewal and Asimow, 2019; Kite, et al., 2020; Lichtenberg, et al., 2021b; Dorn and
2023). Lichtenberg, 2021; Gaillard, et al., 2021; Kite and Schaefer, 2021;
Another consequence of heterogeneous accretion models is the Lichtenberg and Krijt, 2021; Schlichting and Young, 2022; Wolf,
implication that rocky planets can experience several magma ocean et al., 2022). Laboratory parameterizations of volatile partitioning
stages throughout their evolution (Elkins-Tanton, 2012). Magma- and solubilities are increasingly being incorporated into the models
gas interactions during magma ocean stages lead to volatile which calls for an effort to contextualize the measurements. In this
outgassing at temperature and compositional conditions related, review, we aim to do just that, such that the synergy between
but not equal, to those inferred for core formation (Zahnle, et al., laboratory investigations and astronomical characterizations of
2010; Hirschmann, 2016; Dasgupta and Grewal, 2019; Lichtenberg, hot exoplanets can be maximized.
2022). Volatiles are, by their nature, prone to partitioning into the
gas; accordingly, an increasing effort is being invested into
developing models to account for the atmospheres of accreting 2 Metal-silicate partitioning
planets as large volatile reservoirs, effectively limiting
incorporation into magma oceans or partitioning into cores 2.1 Parameterizing experiments
during planetary accretion. Factors such as oxygen fugacity and
magma ocean depth and volatile content strongly affect the resulting In addition to gravitational segregation, core-mantle
atmosphere and residual mantle compositions (Hirschmann, 2016; differentiation in terrestrial planets can be thought of in terms of
Grewal, et al., 2021b; Gaillard, et al., 2021; Jackson et al., 2021). the chemical separation of core Fe from mantle oxides and silicates.
Models are now being developed to account for the distribution of Thus, laboratory experiments study the chemical transfer of relevant
volatile elements into atmospheres with varying thermodynamic species between metal alloys and silicate/oxide mixtures. The
and compositional properties (Salvador, et al., 2017; Nikolaou, et al., parameterization of metal-silicate partitioning reactions and
2019; Lichtenberg, et al., 2021b; Bower, et al., 2022). Although experimental results has been covered extensively in several
solubility establishes the equilibrium distribution of a volatile recent works (Wood, et al., 2006; Corgne, et al., 2008a;
element between a primordial atmosphere and its underlying Blanchard, et al., 2017; Huang and Badro, 2018; Chidester, et al.,
magma ocean, increasing attention is being paid to how kinetic 2022), and only a brief overview is given here.
processes, including diffusion and convective stirring within The equilibrium partitioning of an element between metal and
planetary interiors, may affect the outgassing and ingassing of silicate can be thought of as an exchange reaction between molten
magma oceans (Salvador and Samuel, 2023). metal (M) and oxide:
Partition coefficients and solubilities are the fundamental data n n
needed to parameterize core-mantle differentiation and magma MO n2 + Fe <  > FeO+M (1)
2 2
ocean-atmosphere exchange models. These parameters have been
incorporated into models that are used to understand how volatile where n is the valence of element M. At equilibrium, the partition
elements are fractionated and cycled among major planetary coefficient D is the ratio of the concentration (here in terms of molar
reservoirs—i.e., cores, mantles, and atmospheres—for a range of fraction X, but can also be in terms of weight percent, wt. %) of an
bodies, including Earth, Mars, Venus, and differentiated element in the metal phase to that in the silicate phase:
planetesimals such as the parent bodies of iron meteorites XM
DM  (2)
(Hirschmann, 2012; Wordsworth, 2016; Gaillard, et al., 2021; XMOn/2
Jackson et al., 2021; Li, et al., 2021; Grewal, et al., 2022a;
Lichtenberg, et al., 2022; Grewal and Asimow, 2023). Although The partition coefficient is related to exchange coefficient of the
early models were tuned and benchmarked to the Earth, the reaction, KD, by normalizing by the partition coefficient for Fe:
parameterization made available by recent partitioning and DM
solubility measurements allows the models to be adapted to a KD (M)  (3)
Dn/2
Fe
wide range of other planetary formation scenarios. Thousands of
rocky exoplanets have been discovered by surveys such as the Kepler That is, KD is the ratio of the partition coefficient of element M to
Mission (Batalha, 2014) and the Transiting Exoplanet Survey that of iron and is independent of the Fe concentrations during the
Satellite (Kaltenegger, et al., 2019), and atmospheres of super- reaction.
Earths and sub-Neptunes are now being characterized by the KD is related to the equilibrium constant K of reaction (1), which
James Webb Space Telescope (JWST) (Mansfield, et al., 2019; can be defined in terms of KD and the activity coefficient (γ) of the
Ding and Wordsworth, 2022). In particular, in its first year of metal and silicate phases (E.g., Chidester, et al., 2022):
observations, JWST has demonstrated its capabilities to constrain
silicate n/2
the presence or absence of large volatile envelopes around short- γmetal
γFeO 
log K(M)  log KD (M) + log M
n/2 + log silicate
period rocky exoplanets (Greene, et al., 2023; Ih, et al., 2023; Moran, metal

γFe 
γMOn/2
et al., 2023; Zieba, et al., 2023). After reasonable observational times
b P
over the next few observational cycles, JWST will be able to constrain a+ +c (4)
T T
models of the volatile contents and redox states of individual rocky
exoplanets (Kempton, et al., 2023; Piette, et al., 2023). It is therefore Note that the oxygen fugacity of the experiments can be
crucial to continue efforts to model the formation and evolution of expressed in terms of the Fe–FeO equilibrium: Fealloy + 1/2 O2 =

Frontiers in Earth Science 03 frontiersin.org

Suer et al.
FeOsilicate melt, i.e., the Iron-Wüstite (IW) redox buffer (E.g., Corgne,
et al., 2008a; Campbell, et al., 2009; Chidester, et al., 2022):
aFe γ XFe
ΔIW −2log10  −2log10 Fe
aFeO γFeO XFeO
Where a in this case refers to the activity.
For reaction (1), K is related to the Gibbs free energy of the
reaction (E.g., Chapter 11 of Ganguly, 2008):
ΔGo ΔHo − TΔSo + PΔVo
log K(M) −  (6)
RT RT
where R is the gas constant, T temperature, P pressure, and ΔHo,
ΔSo, and ΔVo are the changes in enthalpy, entropy, and volume of
reaction (1), respectively. The natural log of the partition coefficient,
log D(M) can then be expressed in terms of the above variables and
constants:
b P ΔIW γmetal
log D(M)  a + +c −d − log M
T T 2 metal n/2

γ  Fe
The constants a, b, c, and d are determined using multivariate
least-squares linear regression of the measured Ds, Ps, Ts, and
compositions. The parameterization can also include activity
terms for the light components in the alloy and silicate melt
polymerization. The expression obtained from the regression can
then be used to determine partition coefficients over a wide
P-T-f O2-X space, although care must be taken when regressing
because a, b, and c may significantly change with variations in
experimental conditions (Walter and Cottrell, 2013). By coupling
these functions to core formation models, we can calculate the re-
distribution of elements between cores and mantles during
differentiation.
2.2 Core formation models
In the single-stage core formation model, a planet is assumed to
differentiate instantaneously and the re-distribution of a chemical
species between core and mantle is determined at one set of
conditions. Using the formalism of (Rudge, et al., 2010), the
mass of species c in the body is conserved as follows:
xb  Fxce + (1 − F)xme
where xb is the bulk composition, xme is the concentration in the
mantle embryo, xce is the concentration in the core of the embryo,
and F is the body’s core mass fraction, which varies in the Solar
System from 0.25 (Mars) to 0.8 (Mercury). The effective partitioning
Dx in the embryo is defined at one set of P-T-X conditions and
assumed constant in single-stage models:
xce
Dx  (9)
xme
In multi-stage core formation models, partition coefficients
evolve with the magma ocean depth to account for multiple or
continuous differentiation events (Rubie, et al., 2003). The
conservation of mass of species x into the accreting planet’s core
and mantle can integrated numerically from Eqs 9, 10 following
from Rudge et al. (2010). Similar formalisms are also developed
elsewhere (Rubie, et al., 2011):
Frontiers in Earth Science
10.3389/feart.2023.1159412
d dM
((1 − F)Mxm )[(1 − F)xme + kF(xce − DX xm )] (10)
dt dt
d dM
(5) (FMxc )[kFDX xm + (1 − k) Fxce ] (11)
dt dt
where xm and xc are the concentrations of species x in the mantle and
core respectively of the resultant body. M is the mass of the Earth
which changes with time t. Dc evolves with P-T-f O2-X conditions as
the planet accretes. This framework can be adapted to different
evolution and accretion paths, including accreting bodies of
different sizes and compositions and varying degrees of metal-
silicate equilibration between impactors and the magma ocean.
The first term on the right-hand side of Eq. 10 represents
material from the embryo’s mantle that is added to the Earth’s
mantle, whereas the second term represents the mantle that re-
equilibrated with the impactor core. Partial equilibration due to
inefficient mixing between large impactors towards the end of
(7) accretion (Rubie, et al., 2003; Dahl and Stevenson, 2010) is
introduced by the parameter k, which is the fraction of the
embryo’s core that equilibrates with the planet’s mantle. The
expressions on the right-hand side of Eq. 11 represent the two
paths that the metal can take to the core: (1 − k) Fcce is the fraction of
the embryo’s core that is added directly to the planet’s core whereas
kFDxcm is the fraction that equilibrates with the mantle.
Alternatively, partial equilibration can be implemented using a
turbulent mixing parameterization derived from fluid dynamic
experiments (Deguen, et al., 2014), which is identical in terms of
mass conservation to the approach of Rudge et al. (2010), but the
single fraction k is replaced by an efficiency factor ξ:
k
ξ (12)
1 + DΔX
where Δ is a metal dilution ratio that is related to the relative
densities of the equilibrating metal and silicate (Deguen et al., 2014).
2.3 Metal-silicate partitioning behaviors of
the volatile elements
The effect of core formation on the distribution of volatile
elements has primarily been investigated through metal-silicate
(8)
partitioning experiments at conditions relevant to small
protoplanets and terrestrial planet embryos (0.5 GPa ≤ p ≤
20 GPa and T up to 2500 K) in large-volume press studies
(Dasgupta, et al., 2013; Roskosz, et al., 2013; Boujibar, et al.,
2014; Chi, et al., 2014; Stanley, et al., 2014; Li, et al., 2015; Li,
et al., 2016a; Li, et al., 2016b; Dalou, et al., 2017; Clesi, et al., 2018;
Speelmanns, et al., 2018; Tsuno, et al., 2018; Grewal, et al., 2019a;
Grewal, et al., 2019b; Dalou, et al., 2019; Kuwahara, et al., 2019;
Malavergne, et al., 2019; Grewal, et al., 2021a; Grewal, et al., 2021b;
Fichtner, et al., 2021; Jackson et al., 2021; Kuwahara, et al., 2021;
Zhang and Li, 2021; Grewal, et al., 2022a; Grewal, et al., 2022b; Shi,
et al., 2022; Grewal and Asimow, 2023). More recently, experiments
performed in laser-heated diamond anvil cells (DACs) have
extended the P-T range of measurements on volatile elements to
the average conditions thought to be relevant to core formation in
the Earth and beyond (20 GPa ≤ p ≤ 108 GPa, and T up to ~5500 K)
(Roskosz, et al., 2013; Suer, et al., 2017; Fischer, et al., 2020; Jackson
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TABLE 1 Recommended values of volatile element partition coefficients (Dx) over a range of P-T-f O2-X conditions relevant to different magma ocean depth/
planetary size and redox conditions. Functional forms from the literature are used to calculate these partition coefficients, see Supplementary Appendix SA (H
(Malavergne, et al., 2019; Tagawa, et al., 2021), N (Grewal, et al., 2021b), C (Malavergne, et al., 2019; Fischer, et al., 2020; Blanchard, et al., 2022), S (Boujibar, et al.,
2014; Suer, et al., 2017). Note that these recommended values based on specific set of conditions and different values will be obtained if conditions/variables in the
functions are changed. Ds are rounded off to the nearest significant decimal. Uncertainties on the Ds are dependent on the uncertainties in the fits to the
functional forms and can be as large as ± 20%.

Planetesimals/shallow magma ocean Embryo/intermediate magma ocean Planet/deep magma ocean

Reduced Oxidized Reduced Oxidized Reduced Oxidized (ΔIW

(ΔIW ~ −4) (ΔIW ~ −1) (ΔIW ~ −4) (ΔIW ~ −1) (ΔIW ~ −4) ~ −1 to ~1.3)
P 5 5 20 20 60 60
(GPa)

T (K) 2000 2000 3,000 3,000 4,000 4,000

DS 3 60 30 183 10 173

DC 316 10 43 1.4 0.5 to 20 0.1 to 6

DH 0.3 0.07 60 1.9 100 30

DN 5 265 1 39 no data no data

et al., 2021; Tagawa, et al., 2021; Blanchard, et al., 2022; Chidester,
et al., 2022). In the following subsections, we discuss these
measurements and their major implications for the distribution
of volatile elements between the cores and mantles of the Earth and
other rocky planets during their formation. We also provide
recommended values of metal-silicate partition coefficients for a
range of planetary formation scenarios (See Table 1 and details in
Supplementary Appendix SA).
2.3.1 Hydrogen
Hydrogen is the most cosmochemically abundant of the
volatile elements and is found in significant concentrations in
a wide range of meteorites (Alexander, 2019a; Alexander, 2019b;
McCubbin and Barnes, 2019; Lewis, et al., 2022; Peterson, et al.,
2023). The D/H ratios of various terrestrial, meteoritic, and
planetary reservoirs have been crucial in constraining the
origins of hydrogen on Earth, which measurements indicate
could be due to contributions from different reservoirs
accreted at different times throughout the Solar System’s
history (Albarede, et al., 2013; Halliday, 2013). Studies of
hydrogen metal-silicate partitioning behavior (and solubility,
discussed in section 3.1.1) have recently become important in
the context of sub-Neptune exoplanets, which are thought to
have retained thick primodrial H and/or He envelopes (Fulton,
et al., 2017; Lichtenberg, et al., 2021a; Dorn and Lichtenberg,
2021; Rogers and Owen, 2021; Schlichting and Young, 2022).
There is also isotopic evidence that the Earth and Mars could
have had an early H-rich atmosphere (Tian, et al., 2005; Sharp,
2017; Pahlevan, et al., 2022). Hydrogen could also have been
ingassed into Earth’s magma ocean if it was in contact with such
an atmosphere, and may have ultimately partitioned into the core
(Wu, et al., 2018; Young, et al., 2023). Likewise, the cores of
H-rich exoplanets could also have inherited nebular H, which
would have influenced their total water abundances (Kimura and
Ikoma, 2022).
Though hypothesized to be a low-density core component, its
tendency to diffuse and exsolve makes measuring the metal-silicate
partitioning of hydrogen difficult, and data remain sparse (See
compilation in Figure 1); it readily forms FeHx at pressures
above 5 GPa, but decomposes at ambient conditions (Badding,
et al., 1991; Okuchi, 1997). Okuchi (1997) indirectly (i.e., by
estimating the volume of gas bubbles) determined DH at 7.5 GPa
and 1,200°C–1,500°C in large-volume press experiments to be ~1 on
average and proposed that H could be a primary light element in
Earth’s core. More recently, large-volume press experiments have
yielded new estimates for DH up to 20 GPa, as constrained by a
combination of analytical techniques including electron probe
microanalysis (EPMA), nuclear microprobe resonance (NMR),
and electron recoil detection analysis (ERDA) inferred from the
latter experiments (Clesi, et al., 2018; Malavergne, et al., 2019).
Resultant DH values from these two studies are lower than unity
(lithophile behavior), but thermodynamic modeling also suggested
that higher pressure conditions could make H more siderophile. It is
important to note that these studies measured sample compositions
after quenching, and it is possible that hydrogen diffused out of their
quench products, leading to large biases on DH. Carbon saturation in
the metals of the latter experiments could also have contributed to
lowering DH.
Measurements in laser-heated DAC experiments indirectly
inferred H content from the unit cell expansion with in situ X-ray
diffraction (Tagawa, et al., 2021) and found H to be siderophile, with
DH > 29 at 30–60 GPa and 3,100–4600 K, in agreement with
theoretical calculations (Yuan and Steinle-Neumann, 2020). When
coupled with a core formation model, those values imply that up to
0.6 wt. % H could have been incorporated into the Earth’s core
and >0.15 wt. % into the cores of planets more massive than
0.1ME if water was accreted during the main stage of accretion.
2.3.2 Carbon
The presence of carbon in Earth’s and other planetary cores has
been inferred from its affinity for iron at ambient conditions and its
depletion in the BSE relative to carbonaceous chondrites (CIs)
(Hirschmann, 2016). The results of metal-silicate partitioning
experiments at pressures up to 15 GPa in large-volume presses
(Dasgupta, et al., 2013; Chi, et al., 2014; Malavergne, et al., 2019)
indicate that although carbon is a highly siderophile (DC up to 105)

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FIGURE 1
Hydrogen partition coefficients (log DH) plotted as a function of oxygen fugacity, parameterized here in terms of the iron-wüstite (ΔIW) buffer (A) and
experimental temperature (B). Data sources: (Okuchi, 1997; Clesi, et al., 2018; Malavergne, et al., 2019; Tagawa, et al., 2021).

FIGURE 2
Carbon partition coefficients (log DC) plotted as a function of oxygen fugacity, parameterized here in terms of the iron-wüstite (ΔIW) buffer (A) and
experimental temperature (B). Data sources: (Dasgupta, et al., 2013; Chi, et al., 2014; Armstrong, et al., 2015; Li, et al., 2016b; Dalou, et al., 2017; Tsuno,
et al., 2018; Grewal, et al., 2019a; Kuwahara, et al., 2019; Malavergne, et al., 2019; Fischer, et al., 2020; Grewal, et al., 2021a; Fichtner, et al., 2021;
Blanchard, et al., 2022).

at lower pressures conditions (~1 GPa), it will partition significantly
less into Fe as pressure increases (e.g., DC ≈ 10 at 15 GPa) (See
compilation in Figure 2). Models based on these results, suggest that
the cores of smaller planetesimals could retain wt. % levels of carbon,
whereas those of larger bodies would be less enriched (<1 wt. % C)
while their mantles would become progressively more C-rich during
accretion (Kuwahara, et al., 2021). Though DC can increase as fO2
decreases from ΔIW −1 to −3 (Malavergne, et al., 2019), under
highly reducing conditions, Si will partition strongly into iron,
limiting C dissolution in cores of very reduced bodies. This
chemical trend has led to the suggestion that the Ureilite parent
body or Mercury could have become carbon-saturated, possibly
leading to a graphite-rich crust (Vander Kaaden and McCubbin,
2015; Keppler and Golabek, 2019; Steenstra and van Westrenen,
2020). The presence of sulfur and nitrogen in core materials can also
affect the partitioning of carbon into the Fe (Grewal, et al., 2019b;
Jackson et al., 2021), and immiscible C- and S-rich layers could have
been contemporaneous in the cores of some planetesimals (Corgne,
et al., 2008b).
Experimental results at higher P-T conditions in laser-heated
DACs show that carbon has a lowered affinity for iron at the
conditions of a deep terrestrial magma ocean (Fischer, et al.,
2020; Blanchard, et al., 2022). When coupled with models of
Earth’s core formation and accretion, these partition coefficients
imply that less than 1 wt. % C could be present in the cores of Earth
and similar-sized bodies. Complementary mantle compositions
could be hundreds of ppm, depending on the timing of carbon
accretion.
2.3.3 Nitrogen
Nitrogen is the most abundant component of Earth’s
atmosphere and its presence in meteoritic material indicates that

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Suer et al.
FIGURE 3
Nitrogen partition coefficients (log DN) plotted as a function of oxygen fugacity, parameterized here in terms of the iron-wüstite (ΔIW) buffer (A) and
experimental temperature (B). Data sources: (Roskosz, et al., 2013; Li, et al., 2015; Dalou, et al., 2017; Speelmanns, et al., 2018; Grewal, et al., 2019a;
Grewal, et al., 2019b; Dalou, et al., 2019; Grewal, et al., 2021b; Jackson et al., 2021; Shi, et al., 2022).
it was present in early planetary building blocks (Marty, 2012;
Grewal, et al., 2021b; Grewal, 2022; Grewal and Asimow, 2023).
Its depletion in Earth’s mantle relative to C (Marty, 2012) suggests
that N could have been incorporated into the Earth’s core.
Furthermore, it has been noted from early solubility experiments
that N is increasingly incorporated into iron with increasing
pressures of up to 7 GPa (Roskosz, et al., 2013; Speelmanns,
et al., 2018). More recent metal-silicate partitioning experiments
in large-volume presses (Dalou, et al., 2017; Grewal, et al., 2019a;
Dalou, et al., 2019) found N to be siderophile (10 < DN < 31) at
1–7 GPa and up to 1800°C (See Figure 3); its partitioning behavior
being sensitive to P, T, f O2, and the presence of light elements such
as S in Fe (Grewal, et al., 2019a). The sensitivity of N partitioning to
oxygen fugacity suggests that it dissolves as nitride (N3−) in silicate
melts and as neutral N in core metals (Dalou et al., 2019; Grewal
et al., 2020), and this change in oxidation state makes N partitioning
relatively sensitive to oxygen fugacity compared to the other volatile
elements.
Nitrogen is poorly soluble in magmas at oxygen fugacities
around IW (Libourel et al., 2003). Thus, magmatically active
bodies can lose a large fraction of their N to their atmosphere.
Combined differentiation, outgassing, and accretion models show
that protoplanets that differentiated early could have been depleted
in N (Grewal, et al., 2021b). However, if differentiation occurred
later at the embryonic stage, nitrogen reservoirs could have been
maintained within cores while the mantles would have remained
depleted, a scenario which could explain the N signature of the
terrestrial mantle (Grewal, et al., 2021c). Limited laser-heated DAC
data demonstrate that N remains siderophile up to 26 GPa and
~3500 K (Jackson et al., 2021), further suggesting that it could be
sequestered into larger planetary cores. This behavior is qualitatively
different from C and S, which both become less siderophile at
increased pressures and temperatures. This change in siderophile
behavior among the volatile elements has significant implications for
the S-C-N reservoirs on planetary embryos and larger planets
(Jackson et al., 2021). The measurements compiled in Figure 3
highlight that DN increases with increasing f O2. Obtaining
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measurements at higher P-T conditions will be valuable to
further investigations of N incorporation into the cores of large
planets.
2.3.4 Sulfur
Sulfur’s affinity for iron at ambient conditions and its presence
in iron meteorites imply that it could be a component of
protoplanets and planetary cores (Dreibus and Wanke, 1985;
Chabot, 2004; Gounelle and Zolensky, 2014). Combined with its
cosmochemical abundance, these factors have been used to argue
that S is one of the light alloying components in Earth’s and other
planetary cores. Its incorporation into Fe has been studied
extensively in an attempt to explain the density deficit in Earths’s
core (i.e., relative to that of pure iron) and the properties of other
planetary cores (Fei, et al., 1995; Morard, et al., 2013; Boujibar, et al.,
2020; Brennan, et al., 2020). S is also known to affect the behaviors of
other chemical species in various geological settings, particularly
chalcophile elements (Jana and Walker, 1997; Mahan, et al., 2018)
and C (Li, et al., 2016b; Tsuno, et al., 2018). Experiments in large-
volume presses up to 30 GPa (Li and Agee, 2001; Boujibar, et al.,
2014); showed the increasing siderophile tendency of S with
increasing pressure, lending support to its incorporation into the
cores of planetesimals and planetary embryos. For example, Mars,
which is the size of a planetary embryo and more volatile rich than
Earth, could contain up to ~20 wt. % S in its core (Brennan, et al.,
2020) while it has been speculated that Mercury’s core could be
surrounded by an FeS layer (Namur, et al., 2016). Experiments in
laser-heated DACs ~29–100 GPa, up to 5300 K (Suer, et al., 2017;
Mahan, et al., 2018; Jackson et al., 2018; Chidester, et al., 2022);
found DS values that are an order of magnitude lower on average
than large-volume press results (ranging from less than 10–100),
suggesting that sulfur’s siderophile tendency does increase with
pressure, but is also strongly suppressed at high temperatures
(see compilation in Figure 4). When the results of laser-heated
DAC experiments are included in fitting the functional form for log
DS, the entropy term is an order of magnitude larger than if the fit
included only the large-volume pressure cell results. This is generally
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FIGURE 4
Sulfur partition coefficients (log DS) plotted as a function of oxygen fugacity, parameterized here in terms of the iron-wüstite (ΔIW) buffer (A) and
experimental temperature (B). Data sources: (Li and Agee, 1996; Ohtani, et al., 1997; Wade and Wood, 2001; Chabot and Agee, 2003; Wood, 2008; Mann,
et al., 2009; Rose-Weston, et al., 2009; Boujibar, et al., 2014; Suer, et al., 2017; Mahan, et al., 2018; Jackson et al., 2021; Chidester, et al., 2022).
the case with laser-heated DAC studies of other elements. Redox and
the chemical speciation of S have also been shown to play an
important role in its partitioning behavior (Mavrogenes and
O’Neill, 1999; Chidester, et al., 2022).
When the functional form for DS is incorporated into models of
Earth’s core formation (Boujibar, et al., 2014; Suer, et al., 2017), less
than 2 wt. % S can partition into the core, in agreement with
cosmochemical (McDonough and Sun, 1995) and geophysical
constraints (Badro, et al., 2014). However, depending on the
initial bulk sulfur content and/or the timing of sulfur accretion
and the efficiency of core-mantle equilibration, more sulfur could be
incorporated into planetary cores. Predicted sulfur compositions of
the Earth’s mantle could range from a few hundred to thousands of
ppm also depending on the timing of sulfur accretion (Rubie, et al.,
2016; Suer, et al., 2017), overlapping with geochemical observations
suggesting that the BSE contains ~200 ppm S (McDonough and Sun,
1995; Wang and Becker, 2013). It is possible that magma ocean
crystallization leads to an increase in S concentrations (Rubie, et al.,
2016). Above the sulfur capacity at sulfide saturation (SCSS) limit,
precipitation and segregation of a sulfide-rich matte could occur on
a planet-wide scale in both small and large bodies (O’Neill and
Mavrogenes, 2002; Steenstra, et al., 2020), leading to a late pulse of
core formation if the sulfide phase can mobilize to the core-mantle
boundary.
2.4 Experimental limitations
In the last decade, advances in experimental and analytical
techniques have enabled high-quality measurements of metal-
silicate partitioning coefficients and the solubilities of volatile
elements. Nonetheless, the interpretation of some of these
measurements remain controversial.
Although not specific to volatile-element partitioning,
ambiguity surrounds the interpretation of quench textures in
both large-volume press and DAC experimental samples.
Dendritic textures and overgrowths of quench rims in run
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products of large-volume press experiments lead to difficulty in
determining stable liquid compositions. Likewise, the origin of
metallic inclusions in the silicate portions of DAC run products
has been controversial. Figure 5 shows examples of a large volume
and laser-heated DAC experiment post quench. Large metal
inclusions are usually excluded from analyses of silicate melt
compositions, but smaller nanoscale inclusions (nanonuggets) are
difficult to avoid, particularly with EPMA which integrates over
several to tens of cubic microns. To assess this issue, NanoSIMS has
been used to obtain highly resolved measurements for S and C (Suer,
et al., 2017; Fischer, et al., 2020; Blanchard, et al., 2022). TEM
measurements have also been performed to help resolve this
controversy in recent studies (Fischer, et al., 2015; Suer, et al.,
2017; Suer, et al., 2021), which suggest that nanoparticles form upon
rapid quench but were dissolved during equilibrium melting.
However, if nano-metal inclusions are contaminants, they could
lower measured partition coefficients for the volatiles and other
elements, significantly impacting the results of models that utilize
these measurements.
De-volatilization and the loss of volatile species during
quenching can lead to large uncertainties on experimental
measurements. The degree to which a high pressure-high
temperature assemblage is preserved depends on the quench rate
of the experimental apparatus: example quench rates are 175°C/s in
piston-cylinder experiments, ~800°C/s in multi-anvil experiments,
and thousands of degrees per microsecond in DAC experiments.
Magnesium-rich silicates (analogs of mafic terrestrial magma
oceans) are difficult to quench to a homogenous glass, and some
works have thus used basaltic and andesitic silicate compositions
(Suer, et al., 2017). Quenching is particularly important for
hydrogen, which is known to escape from silicate melts and
metals upon recovery at ambient conditions (Okuchi, 1997).
Therefore, it has been particularly difficult to obtain reliable
partitioning measurements for hydrogen. Recently, the
combination of EPMA, NMR and ERDA have been used
successfully to measure partition coefficients for H and C (Clesi,
et al., 2018; Malavergne, et al., 2019).
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FIGURE 5
Scanning electron microscope images of quench products from metal-silicate partitioning experiments on a large-volume press (A) (Dalou, et al.,
2017) and laser-heated diamond anvil cell (B). Bright regions indicate material with higher atomic number such as Fe-Ni alloys. The quenched silicate
regions of both samples contain small inclusions. In the case of diamond anvil cell experiments, inclusions can be as small as the nanometer scale.
The large concentrations of volatile elements used in the iron
alloys of some experiments can also affect partition coefficients.
Such concentrations are typically much higher than those observed
in nature and can be in violation of Henry’s law. Thus, the
application of such partition coefficients in models may
introduce additional, and difficult to quantify, uncertainties
(Kuwahara, et al., 2019; Grewal, et al., 2021a; Grewal, et al.,
2022b; Shi, et al., 2022).
Statistical regressions of measurements are used to obtain
constants for the functional description of partitioning behavior.
Differences have been noted between partitioning behaviors in
large-volume press and DAC experiments. These have been
attributed to changes in chemical behaviors in the different P-T
regimes probed by these two types of apparatuses. This effect is
perhaps best documented for S and can be seen in the different
magnitudes of the regression constants obtained across different
experimental techniques (Boujibar, et al., 2014; Suer, et al., 2017).
Thus, a single functional form might not be sufficient to fully
describe datasets spanning large P-T ranges. In addition, linear
functional relationships might not fully describe the convolution
of the IW redox buffer with the behaviors of other elements
involved, and further modeling efforts are needed to deconvolve
these effects. For these reasons, it is not recommended that the
functional forms be extrapolated beyond the ranges of the
measurements on which they are based.
3 Volatile element solubilities and
magma-atmosphere interactions
Volatile elements distribute themselves between metal, silicate,
and gas during planetary formation (Chao, et al., 2021; Lichtenberg,
et al., 2022). Metal reacts with magma before its segregation to the
core, whereas gas and magma continuously exchange volatiles at the
atmosphere-magma ocean interface. Thus, it is expected that
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planetary bodies continuously redistribute their volatile element
budgets as they grow and undergo new periods of core formation
and mantle melting. In the previous section, our focus was on the
sequestration of volatile elements within planetary cores via metal
segregation in magma oceans. In this section, however, our focus is
to understand how the presence of an atmosphere can affect the
distribution of volatile elements during core formation, because any
gaseous molecule present in an atmosphere subtracts from the
budget available to metal-silicate partitioning.
3.1 Gas solubilities in magma oceans
Solubility is perhaps the most central parameter governing the
chemical interaction of a primordial atmosphere and its underlying
magma ocean. More specifically, solubility quantifies the
relationship between the fugacity of a gas species and its
corresponding concentration in a condensed phase. This can be
expressed as:
X i  f αi Si (13)
where X i is the concentration of element i dissolved in the
condensed phase, f αi is the fugacity of element i in the gas (or
fluid) raised to an exponent that relates to the stoichiometry of the
dissolution reaction(s), and Si is the solubility of element i in the
condensed phase. Solubility depends on the temperature and
pressure of the reaction as well as the compositions of the
condensed and gaseous phases. In our example, the condensed
phase is the magma. Fugacity can be further deconvolved as:
f i  γi Pi (14)
where γi and Pi are the fugacity coefficient and the partial pressure
of element i, respectively. The high temperatures and moderate
pressures in atmospheres suggest that the gases present will only
have moderate deviations from ideality, and fugacity coefficients are
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often assumed to be unity, such that fugacity and partial pressure are
equal. Eqs 13, 14 reveal the overarching role of atmospheric pressure
on atmosphere-magma interactions, as it is partial pressures that
drive the dissolution of volatile species into the magma.
The stability of a gas species depends on the prevailing P-T-X
conditions within the gas phase. For example, the stability of CO
with respect to CO2 can be expressed as:
CO
g + 0.5O2
g  CO2
g (15)
Le Chatelier analysis indicates that more oxidized conditions
favor CO2 stability compared to CO. In isolation, this reaction also
predicts that CO2 will be favored under lower temperature and
higher pressure given that the reactants have higher entropy and
volume, but all major gas species should be considered together
when making specific predictions regarding how species
concentration is affected by changing P-T conditions for any
bulk gas composition.
The example above stresses the importance of oxygen fugacity in
determining the stability of gas species. We note, however, that it is
not precisely known how oxygen fugacity varies throughout a
growing planet. It is known that, at depth, magma oceans are
saturated in liquid Fe alloy and are therefore strongly reduced
environments (well below the IW oxygen buffer, as inferred by
the low residual FeO concentrations in the bulk silicate portions of
planets), but isochemical decompression (or compression) of a
magma can drive homogeneous reactions that cause auto-
reduction or auto-oxidation (Zhang, et al., 2018; Armstrong,
et al., 2019). Moreover, magma ocean crystallization should lead
to fO2 variations given the different partitioning of ferric and ferrous
Fe between minerals and melts. This implies that the oxygen fugacity
associated with metal-silicate reactions need not be the same as that
associated with gas-magma reactions, particularly because the
magma ocean may become increasingly chemically isolated form
the atmosphere as solidification progresses (Bower et al., 2022).
However, our goal is not to review this dynamic and the potential
resulting redox stratification within planetary magma oceans
(Hirschmann, 2012). Rather, we introduce this concept to stress
that a wide range of oxygen fugacities are likely to impact volatile
element solubilities associated with planetary formation. We
correspondingly organize our review of gas solubilities below by
element, and within each element by oxygen fugacity. We also
emphasize that our goal is not to provide an unabridged review
of volatile element solubilities in magmas, but we simply seek to
highlight the basic controls on volatile element solubilities and to
provide reference solubility values that may serve to accelerate the
development of magma ocean-atmosphere interaction models.
3.1.1 Hydrogen
When reacted with oxygen, hydrogen gas forms water as (similar
to Reaction 15):
H2
g + 0.5O2
g  H2 O
g (16)
Relative to H2, gaseous water molecules have a wide stability
field under geological conditions, as demonstrated by the ratio of
f H2O/f H2 plotted as a function of ΔIW at 2273 K (Figure 7A). The
crossover of f H2O/f H2 ratio occurs near IW and is nearly
independent of temperature. We note that we use
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FIGURE 6
Schematic contours of H, C, and N speciation determined by
Raman spectroscopy in basaltic glasses synthesized in piston-cylinder
experiments at 1–2 GPa and 1,400°C–1,600°C, shown as a function of
fO2 (relative to the IW buffer) and H content (as equivalent H2O,
wt. %). Raman and FTIR measurements are from Hirschmann (2012),
Armstrong et al. (2015), Dalou et al. (2019, 2022), and Grewal et al.
(2020). Blank areas represent conditions at which literature data are
currently lacking. This figure demonstrates that H, C, and N on their
own may be present as multiple species at a given fO2 or water
content, and that they combine to form different molecules in natural
and synthetic glasses. fO2 of Earth and Mars formation are indicated.
Sulfur speciation is not shown because the effect of H on S speciation
has not yet been determined at fO2 relevant to magma ocean
conditions.
thermodynamic data from the NIST WebBook to calculate
equilibrium constants of reactions between gases.
Water vapor can dissolve into magma as either OH or H2O
(molecular) following the reactions:
H2 O
g  H2 O (melt) (17)
−2 −
H2 O(melt) + O (melt)  2OH (melt) (18)
Reactions 17 and 18 predict that low f H2O values should favor
the dissolution of OH; however, with increasing OH concentration,
relatively more H2O will dissolve as molecular H2O. Indeed, water
solubility has been experimentally shown to scale with f H2O0.5 at
lower concentrations, but with f H2O at higher concentration. The
transition from OH- to H2O-dominated water solubility typically
occurs at the wt. % level (Stolper, 1982), which requires f H2O >
100 bars, whereas terrestrial planets are typically estimated to
contain between 100 and 1,000 ppm H2O integrated over their
silicate reservoirs, atmospheres, and oceans (Peslier, 2010;
Halliday, 2013). This implies that only modest H2O pressures
could have been present in primordial atmospheres (~1–10 bars
on average), unless large amounts of H were lost from the
atmospheres (Catling, et al., 2001). Moreover, the products in
Reaction 18 are favored at higher temperatures (Nowak and
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FIGURE 7
MAGMASAT predictions of H2O solubility in an ultramafic melt at
different temperatures. The curve is fit to the 2273 K data and is given
by Eq. 19.
Behrens, 1995), and, given that magma oceans exist at higher
temperatures than modern magmatic systems, it is expected that
OH is a major component of water solubility in growing planets,
even under relatively reducing conditions (Figure 6).
Hydroxyl forms chemical bonds when dissolved in silicate melts,
lowering melt viscosity and implying that water reacts with bridging
oxygens in Reaction 18 to depolymerize the melt network. Magma
ocean liquids are depolymerized, meaning that they have few
bridging oxygens to support OH dissolution. Studies of water
solubility in depolymerized liquids highlight that water also
bonds with non-bridging oxygens, preferentially forming
complexes with higher field strength cations (Mysen and Virgo,
1986; Xue and Kanzaki, 2004). It is therefore expected that water
should dominantly dissolve as OH at the low fH2O conditions
relevant to magma ocean liquids. A recent work suggests that
peridotitic magmas contain relatively more OH than H2O
compared to more polymerized magmas at equal total H2O
contents, such that H2O solubility in peridotite liquids will
remain dominated by OH up to 5 wt. % H2O (Bondar, et al., 2023).
Experimental determinations of water solubility in magma
oceans have historically been precluded by difficulties associated
with working in ultramafic systems, although recent advances in
rapid-quench multi-anvil and laser levitation techniques are highly
promising (Bondar, et al., 2023; Sossi, et al., 2023). In the absence of
well-established data, we rely on models that allow for the P-T-X
dependencies of water solubility determined within the realm of
quenchable liquids to be extrapolated to the P-T-X realm of magma
oceans. Several models have been developed (Newman and
Lowenstern, 2002; Papale, et al., 2006; Iacovino, et al., 2021), and
we use MAGMASAT (Ghiorso and Gualda, 2015) for our example
because it is implemented in the popular MELTs algorithm and
considers both OH and H2O dissolution.
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Figure 7 plots predicted H2O solubilities from MAGMASAT for
a peridotitic liquid (BSE of (McDonough and Sun, 1995) as a
function of PH2O (assumed ideal) and temperature. Solubility
scales close to PH2O0.5 and is essentially independent of
temperature, although recent experimental data suggest that
water solubility decreases with temperature. Fitting all predictions
together yields the following equation:
H2 Owt.%  0.0575·PH2 O0.5158 (19)
with PH2O in bars. The fact that MAGMASAT predicts that H2O
solubility scales close to PH2O0.5 is consistent with OH dominating
solubility up to 0.6 wt. % H2O dissolved in peridotitic magma.
Such predictions require significant extrapolation because most
water solubility determinations are limited to basaltic (or move
evolved) compositions and typical magmatic temperatures
(<1673 K) and should therefore be treated with caution.
Nevertheless, it is clear that, relative to other gases (see following
subsections), water vapor remains highly soluble in ultramafic
magma, even under magma ocean conditions.
Support for MAGMASAT model prediction comes from recent
results from a laser levitation apparatus study (Sossi, et al., 2023).
This apparatus enables quenching of ultramafic glasses reacted with
controlled f H2O at temperatures that are directly applicable to
magma oceans. Current data collected in systems with f H2O/
f H2 > 1 yield a similar solubility relationship to that predicted above:
H2 Owt.%  0.0605·PH2 O0.47 (20)
assuming a molar absorption coefficient (ε3550) of 5.1 m2/mol.
Under more reducing conditions, water vapor is progressively
destabilized to produce H2. Spectral evidence demonstrates that H2
gas dissolves as molecular H2 in magmas (Luth, et al., 1987). As a
neutral, non-polar molecule, H2 is thought to dissolve into the ionic
porosity of the melt structure, following the well-documented
behavior of noble gases (Carroll and Stolper, 1993). The radius of
H2 is similar to that of helium, and indeed, experiments demonstrate
that H2 solubility is also similar to that of helium, at least for basaltic
melts (Hirschmann, 2012). The solubility of helium, or hydrogen,
has not be experimentally investigated in peridotitic liquids, but
their solubilities can be estimated by extrapolating the relationship
of ionic porosity and solubility for helium, assuming that hydrogen
solubility continues to track with helium towards more
depolymerized compositions on a molar basis. To do this, we
apply the algorithm developed for helium solubility in silicate
melt by (Iacono-Marziano, et al., 2010) to estimate H2 solubility
at 1 bar and 2273 K. Taking a melt composition equal to the BSE
yields the relationship:
H2wt.%  4.19 × 10−5 · PH2 (21)
Experiments demonstrate that temperature has a modest effect
on the solubilities of noble gases (Jambon, et al., 1986) although data
are limited to relatively cool conditions compared to those
associated with magma oceans (<1873 K). It has been suggested
that higher temperatures should favor the dissolution of H2 into
magmas (Chachan and Stevenson, 2018; Kite, et al., 2020), and this
effect could be significant given the wide temperature range over
which magma oceans likely exist. The model of (Iacono-Marziano,
et al., 2010) predicts an order of magnitude increase in helium
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solubility upon heating from 1773 to 3272 K, also suggesting the
importance of high temperatures in promoting H2 dissolution into
magmas.
We now apply the solubility laws for H to calculate its
equilibrium distribution between a magma ocean and a
primordial atmosphere. Solving the equilibrium distribution for
any volatile element is accomplished by solving a system of
equations that include the solubility laws, statements of mass
balance, and the equilibrium constants for gas phase equilibria to
define the relative stabilities of gas species as a function of magma
ocean-atmosphere interface P-T-X conditions. Mass balance
statements use total mass as a constraint, but the mass balance
constraint could also be the pressure of a gas species in the
atmosphere or the concentration of the relevant volatile element
in the magma ocean.
To connect solubility laws to mass distribution, melt
concentration is scaled to mass by multiplying concentration by
the mass of the assumed magma ocean. Partial pressure (fugacity) is
scaled to atmospheric mass as:
Px Ar
Mx  (22)
g
where Px is the partial pressure of gas x in the atmosphere, A is the
surface area of the planet, g is the gravitational constant, and r is the
ratio of mass of the volatile element of interest in the gas molecule to
the full mass of the gas molecule (e.g., 1 for H2 and 2/18 for H2O). It
is clear that the distribution of a volatile element depends on the size
of the planet (A), its gravitational field (g), and the depth (or mass) of
the magma ocean, so these also must be specified.
We provide as an example the system of equations needed to
solve the distribution of H. We apply a similar approach for other
volatile elements in their respective sections.
K  PH2 O
f O0.5
2 PH2  (23)
PH2 M MO PH2 O0.5158 M MO
M H 4.19 × 10−5 · + 0.0575 ·
100 100
(24)
PH2 A PH2 OA182 
+ +
g g
where K is the equilibrium constant for Reaction 24, MH is the total
mass of H in the atmosphere-magma ocean system, and MMO is the
mass of the magma ocean. The equilibrium constant is defined by
the P-T conditions selected and the associated Gibbs energy change
for the reaction (calculated from data tabulated on the NIST
WebBook and the ideal gas law). The factors of 100 are required
in the leftmost terms on the righthand side to convert from wt. % to
wt. fraction. The system is solved for the partial pressures of H2 and
H2O (PH2 and PH2O). This assumes ideal gas behavior; high
temperature-moderate pressure systems (hundreds of bars) only
have small deviations from ideality. For example, the fugacity
coefficient of steam is 0.91 at 1073 K and 500 bars (Helgeson and
Kirkham, 1974) and that of CO2 is 1.2 at 1500 K and 500 bars
(Mel’nik, 1972), taking the standard state to be 1 bar. Higher
temperatures serve only to force fugacity coefficients closer to
unity. CO2-H2O mixtures do have excess energies of mixing, but
again, this effect is generally small at the high temperatures and
moderate pressures of volatile-dominated atmospheres overlying
magma oceans. The solution may require iteration between the
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10.3389/feart.2023.1159412
solved pressure of the atmosphere and that assumed to calculate K
until there is agreement.
We note that this approach can also be extended to predict core
chemistry by adding a term that includes a partition coefficient (with
implied P-T-X conditions for metal-silicate chemical exchange)
along with the available masses of silicate and metal to be
reacted to define the mass of the volatile element sequestered in
the core for the specified P-T-X conditions.
Figure 8 plots the distributions of H species between
atmospheres and magma oceans as a function of f O2 (relative to
the IW oxygen buffer at 1 bar) and the total abundance of H. The
temperature dependance of H2 and H2O stability is largely canceled
by referencing f O2 to the IW buffer. For simplicity, we assume a
total atmospheric pressure of 100 bars and a temperature of 2773 K.
An assumed constant total pressure is supported by the relatively
constant and high pressure that C species provide given the
abundance of C in the BSE, as will be demonstrated in the next
subsection.
The crossover for equal partial pressures of H2 and H2O occurs
near ΔIW−1 at 100 bars and 2273 K (Figure 8A). Water (steam) is
much more soluble than H2, and this shifts the crossover point for
equal H2O and H2 concentrations in magma oceans to extremely
reducing conditions (<ΔIW−6), such that H2O may dominate H
dissolution in magma oceans over a wide range of accretion
scenarios despite the higher partial pressures of H2 in
atmospheres (Figure 8B). In all scenarios, the magma ocean
contains more H by mass than the atmosphere (Figure 8C). H
preferentially partitions into the magma ocean under oxidizing
conditions, but as f O2 drops and f H2 rises, the distribution
becomes nearly equal, indicating the increased volatility of H in
reduced systems. The small masses of H in primordial atmospheres
indicate that they have only a small capacity to limit the
incorporation of H into cores and determine the H abundances
of the bulk silicate reservoirs (i.e., materials later derived from the
magma ocean-atmosphere system, that includes mantle, crust,
atmosphere, and oceans).
3.1.2 Carbon
Under high f O2, CO2 is expected to be the dominant C-bearing
gas species (Reaction 15). Spectroscopic results have identified that
C is present as carbonate groups in magmas when reacted with CO2
gas (Mysen and Boettcher, 1975; Fine and Stolper, 1986), and this
observation suggests that the following set of reactions control CO2
solubility in magmas:
CO2
g  CO2 (melt) (25)
−2
CO2 (melt) + O (melt)  CO−2
3 (melt) (26)
From these reactions, C solubility should linearly scale with CO2
fugacity (α = 1 in Eq. 13), at least up to moderate pressures, and
indeed this has been experimentally documented (Dixon, et al.,
1995).
Carbon solubility increases with increasing alkali and alkali
Earth metal contents in magmas, which is consistent with the
stability of carbonate mineral-like complexes in magmas (Lesne,
et al., 2011; Duncan, et al., 2017). Higher temperatures favor the
dissolution of CO2 in the melt as carbonate (Konschak and Keppler,
2014). Relatively large amounts of CO2 (molecular) can also dissolve
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FIGURE 8
Distributions of H between atmosphere and magma ocean as functions of fO2 (ΔIW). Low-H (H equal to a 1 bar atmosphere of H2 or H2O) and high-
H scenarios (H equal to a 10 bar atmosphere of H2 or H2O) are considered. Masses of H in the low-H and high-H scenarios are broadly similar to those
inferred for the bulk silicate reservoirs of terrestrial bodies within the solar system. All scenarios assume an atmosphere of 100 bars total pressure, a
temperature of 2773 K, an Earth-sized planet, and a full mantle magma ocean. (A) Predictions of partial pressures of H2 and H2O gases in equilibrium
with a magma ocean. PH2O is nearly constant across the range of fO2 considered, whereas PH2 increases under more reducing conditions. (B)
Predictions of H species concentrations for magma oceans in equilibrium with partial pressures of gases in (A). (C) Mass ratios of H in the atmosphere
versus H dissolved in magma oceans. Oxidizing conditions force H2O stability and nearly all H to dissolve into magma oceans. Reducing conditions enable
a more equal distribution of H between atmosphere and magma ocean.

into more evolved (higher SiO2) melt compositions, following

Reaction 25. Higher temperatures also favor reactants in Reaction
25 (Konschak and Keppler, 2014), and it is therefore possible that
molecular CO2 contributes to CO2 solubility within magma oceans.
Sufficient experimental data have been collected to permit the
development of models for CO2 solubility in magmas (Dixon and
Stolper, 1995; Papale, et al., 2006; Iacono-Marziano, et al., 2012). We
again apply MAGMASAT to predict CO2 solubility in peridotitic
liquids over magma ocean P-T conditions (Gualda and Ghiorso,
2015) (Figure 9). Solubility scales with PCO2, as suggested by
Reactions 25 and 26 MAGMASAT predicts that higher
temperatures are predicted to decrease solubility, but the effect is
relatively minor, with solubility decreasing by a factor of 2 between
1,500 and 3000 K. Experimental work on mafic systems also
supports a relatively small effect of temperature; although there is
evidence that CO2 solubility increases with increasing temperature,
this is opposite to the predictions of MAGMASAT. Least squares
fitting of MAGMASAT predictions of CO2 solubility at 2273 K for 1,
10, 50, and 100 bars yields the following relationship for a BSE
FIGURE 9
magma composition: MAGMASAT predictions of CO2 solubility in an ultramafic melt as
CO2wt.%  2.14 × 10−4 · PCO2 (27) a function of PCO2 at different temperatures. The line is fit to the
2273 K data and is given by Eq. 27.
Under more reducing conditions, f CO2 will decrease while f CO
increases for any given temperature and pressure. With decreasing
f CO2, the carbonate and CO2 contents of a magma will without Fe, reacted with variable f CO have not found additional
correspondingly decrease, while C species associated with the evidence that Fe-carbonyl is a significant component of C solubility.
dissolution of CO will increase. Rather, there is building evidence that single CO groups are the
The exact nature of C species dissolved in magmas in dominant species (Armstrong, et al., 2015; Yoshioka, et al., 2019).
equilibrium with CO remains relatively uncertain. Higher than These groups may be molecular CO or CO species complexed to
expected C solubilities were observed in reduced, lunar analog other components in the melt. Without a more detailed
melts rich in Fe, leading to the suggestion that Fe-carbonyl understanding for how CO interacts with magma, extrapolation
groups could be a major component of CO solubility (Wetzel, of CO solubility determinations to magma ocean conditions will
et al., 2013). Other spectroscopic analyses of melts, with or introduce some uncertainty. Nonetheless, it is clear that C becomes

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Suer et al.
less soluble in magma as f CO2 falls and f CO rises. Yoshioka et al.
(2019) developed the following equation to predict the solubility of
C (wt. %) in MORB magmas for a given f CO:
log(Cwt.% ) −5.20 + 0.80log
f CO (28)
The unit for f CO is bar. Note that the solubility of CO is
expressed as reduced carbon, not CO, so statements of mass balance
that incorporate Eq. 28 must take this into account.
The distribution of volatile carbon species between atmospheres
and magma oceans are not predicted to be strongly dependent on
the amount of carbon present in the combined system as the
solubilities of all relevant species scale with their respective
fugacities, with exponents close to unity.
Further decreases in f O2 will progressively destabilize CO,
possibly resulting in graphite/diamond/carbide saturation if
overall C contents are sufficiently high. Decreases in f O2 also
potentially help to stabilize methane or other CH-species if a
source of H is also present (Figure 6):
2H2
g + CO
g  CH4
g + 0.5O2
g (29)
and CH4 can then dissolve into the magma following:
CH4
g  CH4 (melt) (30)
Once dissolved in a magma, methane may undergo further
reactions to produce other hydrocarbon species. Spectroscopic
observations identify CH4, or possibly methyl groups, dissolved
in reduced, H-bearing silicate melts, supporting the importance of
Reaction 29 (Mysen and Yamashita, 2010). Methane presumably
dissolves into the ionic porosity of magma, following the example of
H2 above, but how melt-reactive hydrocarbon species interact with
the silicate network has not been well explored, and their importance
to magma oceans is therefore not as well established as it is for other
species containing C or H.
Figure 10 plots the distribution of C species between
atmospheres and magma oceans as a function of f O2 and the
total abundance of C. Only solubility related to CO2 and CO is
considered. We again assume a temperature of 2273 K, but total
pressure is now determined by the combined pressure of CO and
CO2. Atmospheric pressure therefore decreases as CO is converted
to CO2 with increasing f O2. We explore a high-C scenario (mass
equivalent of 500 bars of C species in the atmosphere-magma ocean
system) and a low-C scenario (mass equivalent 50 bars of C species
in the atmosphere-magma ocean system). For context, present-day
Venus has an atmosphere that is nearly 100 bars of CO2. The
crossover for partial pressures of CO and CO2 is near IW, but
higher pressures stabilize CO2 gas (Eq. 28) and shift the crossover to
more reducing conditions (Figure 10A). The crossover for the melt
concentration of C related to CO and CO2 dissolution occurs below
IW because CO2 species are more soluble than those related to CO
(Figure 10B). Magma oceans are the larger C reservoir when CO2
dominates solubility, whereas the atmosphere is the larger reservoir
when CO dominates solubility (Figure 10C). The ability of the
atmosphere to dominate the C budget therefore appears
restricted to conditions more reducing than IW.
The discussion above for carbon assumes that the magma ocean
remains undersaturated with respect to solid forms of C. High f CO
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10.3389/feart.2023.1159412
(and f CO2) and reducing conditions promote graphite or diamond
saturation following the general reaction:
CO
g  0.5O2 (melt) + C
crystal (31)
Once stabilized, a buffering phase such as diamond or graphite is
a new volatile reservoir that must be accounted for. The physical
stability of the buffering phase must also be considered. For example,
graphite is expected to be buoyant in magma ocean liquids and could
therefore rise to the surface (Keppler and Golabek, 2019), whereas
volatile elements dissolved in alloys or stabilized in intermetallic
compounds (carbide, nitrides, sulfides) may be dense and could
therefore sink within a magma ocean to ultimately join the core.
3.1.3 Nitrogen
N2 is the dominant N-bearing species in the gas phase above
magma oceans (Boulliung, et al., 2020) independent of fO2 (Dalou,
et al., 2022; Sossi, et al., 2023). However, depending on fO2, the
speciation of N in silicate melts simulating magma ocean conditions
falls into two domains. Under oxidized conditions, N dissolves as
molecular N2 with a valence state of 0 and its solubility is primarily
dependent on pressure following Henry’s Law (Libourel, et al., 2003;
Dalou, et al., 2019; Grewal, et al., 2020; Bernadou, et al., 2021). At
reduced conditions, N dissolves as ions with a −3 valence state
(Libourel et al., 2003; Dalou et al., 2019; Mosenfelder et al., 2019;
Boulliung et al., 2020; Grewal et al., 2020; Bernadou et al., 2021).
Depending on fH2, these ions could either be anhydrous nitrides
(N3−) or hydrous amines (NH2−) and ammonia (NH3) molecules
(Mosenfelder, et al., 2019; Grewal, et al., 2020). N2 and NH3
molecules physically dissolve into the ionic porosity of silicate
melts whereas ionic nitrides and amides chemically dissolve into
the silicate melt network by displacing O2− from the silicate melt
network (Libourel et al., 2003). Whereas N2, NH3, and NH2− species
have been observed by Raman and FTIR (fourier transform
infrared) spectroscopy in quenched silicate glasses (Dalou, et al.,
2019; Mosenfelder, et al., 2019; Grewal, et al., 2020) (Figure 6), the
presence of anhydrous N3− has only been observed by Raman by
Dalou et al. (2022) at very low fO2. N solubility as N2 can be
represented as:
N2
g  N2 (melt) (32)
Even though hydrous N-H species are widely observed in
experimental silicate melts simulating magma ocean conditions,
the dissolution of N solely as N3− can adequately fit the observed
N abundances in reduced silicate melts in both hydrous and
anhydrous conditions, and can be represented as:
3
N2
g + 3O2− (melt)  2N3− (melt) + N2
g (33)
2
The solubility of N as molecular N2 under oxidized conditions
(Eq. 31) scales with fN2 and is independent of fO2, whereas the
solubility of N as N3− under reduced conditions (Eq. 32), in addition
to scaling with (fN2) with an exponent between 0.5 and 0.75.
Although the exact fO2 for the transition of N speciation
depends upon several thermodynamic parameters like T, P, fluid
composition, and melt composition, available evidence suggests that
this transition likely occurs near the IW redox buffer for silicate
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FIGURE 10
Distributions of C between atmosphere and magma ocean as functions of fO2 (ΔIW). Low-C (C equal to a 50 bar atmosphere of CO or CO2) and
high-C scenarios (C equal to a 500 bar atmosphere of CO or CO2) are considered. Masses of C in the low-C and high-C scenarios are broadly similar to
those inferred for the bulk silicate reservoirs of terrestrial bodies within the solar system. All scenarios assume a temperature of 2773 K, an Earth-sized
planet, and a full mantle magma ocean. Atmospheric pressure varies with the total pressure of C-bearing gas molecules. (A) Predictions of partial
pressures of CO and CO2 gases in equilibrium with a magma ocean. PCO2 dominates above IW, whereas PCO dominates below IW. (B) Predictions of C
species concentrations for magma oceans in equilibrium with partial pressures of gases in (A). (C) Mass ratios of C in the atmosphere versus C dissolved in
magma oceans. Under oxidizing conditions, C is nearly equally distributed, but reducing conditions make the atmosphere the dominant C reservoir.

melts applicable to shallow magma ocean conditions (Boulliung 3.1.4 Sulfur

et al., 2020; Bernadou et al., 2021).
The solubility of N in analog magma ocean silicate melts has
been extensively studied by experimental studies over the last two
decades for a wide range of fO2, P, and T conditions. Libourel et al.
(2003) calibrated the two-species model (dissolution of N as N2 and
N3− in oxidized and reduced conditions, respectively) with
experimental data at 1 bar to determine N solubility in basaltic
silicate melts as a function of PN and fO2:
Nppm  0.06PN2 + 5.97PN0.5 −0.75
2 f O2
The first term on the righthand side accounts for N2 solubility,
and the second term accounts for N3− solubility. Bernadou, et al.
(2021) showed that the formalism for N solubility in the silicate melt
represented by Eq. 33 remains almost unaltered from 1 to 3,000 bars
in the C-H-O-N system.
Figure 11 plots the distribution of N as a function of fO2
between atmospheres and magma oceans. We explore a high-N
scenario (mass equivalent of 10 bars of N species in the
atmosphere-magma ocean system) and a low-N scenario (mass
equivalent of 1 bar of N species in the atmosphere-magma ocean
system). Atmospheres start to lose significant N while magma
oceans start to gain significant N below IW (Figure 11A and 9
(center)). Figure 11B shows that there are essentially two regimes
for N: i) above IW, nearly all N resides in atmospheres, as N2 is
relatively insoluble in melts; and ii) below IW −3, nearly all N
resides in magma oceans, demonstrating the highly soluble
nature of nitride complexes. Between these two regimes is a
relatively narrow transition zone, although the fO2 values within
this transitional zones overlap with those inferred for magma
oceans from studies of core formation. Atmospheres are the
largest N reservoir when N2 controls solubility to ~IW −2, but
magma oceans quickly dominate the N budget as fO2 drops.
It has long been known (Fincham and Richardson, 1954) that at
fO2 below the quartz-fayalite-magnetite buffer (<IW +3), S dissolves
as S2− by displacing O2− from the anion sublattice. Therefore, at
oxygen fugacities relevant to magma oceans (generally <IW), S
solubility in the silicate melts can be represented as:
1 1
O2− (melt) + S2
g  S2− (melt) + O2
g (35)
2 2
The equilibrium of this equation can be described as:
(34)
ln
Keq  ln
aS2−  + ln
fO0.5
2  − ln
fS2  − ln
aO 
0.5 2−
(36)
The concentration of O2− anions in the silicate melt greatly
exceeds those of other anions, including S2−. O2− concentration or
activity is assumed to be constant and Eq. 36 can be modified as
(assuming the activity coefficient of S2− to be 1):
1 S2
ln(S) (melt)  ln (CS ) + lnf  (37)
2 fO2
where CS , the sulfide capacity of the silicate melt, is a
pseudoequilbrium constant which is controlled by the
composition of the silicate melt, and primarily by its FeO content
(O’Neill and Mavrogenes, 2002). Using data from previous
experiments carried out at 1 atm in which a gas of known fO2
(between IW −1 and IW +3) and fS2 was equilibrated with silicate
melts, Gaillard et al. (2022) devised an empirical relationship to
determine S solubility in the silicate melts:
26476 1 S2
ln
Sppm  13.84− +0.12FeOwt. % (melt) + lnf  (38)
T 2 fO2
It should be noted that this equation is calibrated for FeO-rich
terrestrial basalts with relatively simplified silicate melt
compositions. Although new empirical models have been

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FIGURE 11
Distributions of N between atmosphere and magma ocean as functions of fO2 (ΔIW). Low-N (N equal to a 1 bar atmosphere of N2) and high-N
scenarios (N equal to a 10 bar atmosphere of N2) are considered. Masses of N in the low-N and high-N scenarios are broadly similar to those inferred for
the bulk silicate reservoirs of terrestrial bodies within the solar system. All scenarios assume a temperature of 2773 K, an Earth-sized planet, and a full
mantle magma ocean. (A) Predictions of partial pressures of N2 gas in equilibrium with a magma ocean. (B) Predictions of N species concentrations
for magma oceans in equilibrium with partial pressures of N2 gas in (C). (C) Mass ratios of N in the atmosphere versus N dissolved in magma oceans. Under
oxidizing conditions, N nearly all N is present in the atmosphere, whereas reducing conditions force nearly all N to dissolve into magma oceans.

calibrated with experimental data for FeO-poor magmas (Namur,
et al., 2016), their utility for atmosphere-magma ocean equilibration
models is limited due the lack of a fS2 term.
The empirical equation has FeO and fO2 terms whose effects
are counteract each other in Fe metal-saturated systems. Because
magma ocean silicate melts are in equilibrium with metal during
core-mantle differentiation, their FeO contents are thought to be
lower than those of terrestrial basaltic magmas. Therefore, below
IW, the effect of the fO 2 term dominates such that the S
solubility in the silicate melt increases at increasingly reduced
conditions.
Sulfur solubility is typically expressed as a function of fS2 (Eq.
37), but S2 is not necessarily the dominant S-bearing gas species over
the P-T-X conditions of magma ocean-atmosphere exchange.
Indeed, S is unique in its tendency to form gas molecules with
other volatile elements. Hydrogen sulfide is produced by S2 when
exposed to elevated fH2, and COS is produced by S2 when exposed to
elevated fCO. This dynamic makes predicting the atmosphere-
magma ocean distribution of S correspondingly more
complicated than for H, C, or N.
Figure 12 plots the stability of S-bearing species for an
atmosphere with 100 bars of total pressure. The gas phase is
10 mol% H, 0.03 mol% S, and the balance is C species.
Temperature is fixed at 2273 K, fO2 ranges between ΔIW −4 and
ΔIW +2. Hydrogen sulfide is the most abundant S-bearing gas,
followed by COS, under reducing conditions, whereas SO2 is most
abundant under oxidizing conditions. S2 remains a minority species
over the entire range of fO2.
Figure 12B plots the mass of S in magma oceans for our nominal
scenario (10 mol% H, 0.03 mol% S, and the balance is C species), a
high-S scenario (10 mol% H, 0.3 mol% S, and the balance C is
species), and a high-H scenario (30 mol% H, 0.03 mol% S, and the
balance C species). The mass of S in the magma ocean is calculated
using Eq. 37. All atmospheres are 100 bars total, and equilibrium is
calculated for 2273 K. The horizontal solid lines bracket estimated S
masses for the BSE in Figure 12B. Sulfur is highly soluble in magmas,
and this manifests as the much larger masses of S dissolved in
magma oceans compared to the equilibrium masses of S present in
atmospheres (Figure 12A).
Eq. 37 assumes that HS−species do not contribute to S solubility,
as the compositional dependence of S solubility does not include a
term related to fH2. With this assumption, the stabilization of H2S
gas with increasing fH2 under reducing conditions acts to make S
more volatile. An example of this is provided in Figure 12 as H
scenario. There is debate as to whether HS−species are significant for
S solubility (Baker and Moretti, 2011), so Eq. 37 may underestimate
S solubility in H2-rich systems. Nevertheless, it is clear that S is
relatively soluble in melts and that primordial atmospheres contain
only a small amount of S.
3.2 Beyond an equilibrium model
The analysis above reviewed solubility laws and mass balance
statements to calculate the equilibrium model for the
distribution of H, C, N, and S between magma oceans and
atmospheres. But this framework is not complete and much
work is needed to make new experimental measurements of
solubility under the P-T-X conditions of magma oceans,
including high temperatures, high pressures, ultramafic melt
compositions, and highly reducing conditions. Nevertheless,
applying an equilibrium model with a single P-T-X condition
for chemical exchange within a system as large and dynamic as a
combined magma ocean and atmosphere must fall short because
P-T-X conditions vary with time and heliocentric location as
planets grow.
As magma oceans cool, the interface temperature with the
atmosphere will change (Lichtenberg, et al., 2021a; Lichtenberg,
et al., 2022). The ability of a magma ocean and atmosphere to
remain in equilibrium relies on mass exchange across their

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FIGURE 12
Distributions of sulfur between atmosphere and magma ocean as functions of fO2 (ΔIW). (A) An example calculation of S gas species partial pressures
for a 100-bar atmosphere with a nominal composition of 10 mol% H, 0.03 mol% S, and the balance is C species at 2273 K. (B) Predicted concentrations of
S (dissolved in magma oceans for a nominal atmosphere, a high-S atmosphere (10 mol% H, 0.3 mol% S, and the balance is C), and a high-H atmosphere
(30 mol% H, 0.03 mol% S, and the balance is C species). The horizontal lines bracket the estimated range of S concentrations in the bulk silicate Earth
(McDonough and Sun, 1995) (C) Mass ratios of S in the atmosphere versus S dissolved in magma oceans. All scenarios predict that most S is present within
magma oceans.

interface, but also the nature and associated kinetics of this
exchange remain areas of study (Salvador, et al., 2017). The
diffusion of volatiles from the interface may be important here,
in addition to the convective patterns of the underlying magma
ocean and its associated timescales and length scales for mixing
(Solomatov, 2007). With continued cooling, magma oceans
crystallize, leading to a new era of evolution in which volatiles
will partition between minerals and melts, depending on the
elemental exchange between the magma and its overlying
atmosphere, and hence the formation of a protocrust (Bower,
et al., 2022). Some minerals may be major hosts for volatiles,
but many likely exclude volatiles from their structures.
Crystallization should therefore lead to net outgassing.
Outgassing may be facilitated by bubble nucleation, bubble
growth, and the diffusion of dissolved volatiles in the magma
towards bubbles (Ikoma, et al., 2018). Again, kinetics may be
important in determining the chemical distribution of volatiles
within the magma ocean-atmosphere system. Crystallization also
offers the possibility of trapping buoyant magmas in the cumulate
piles of magma oceans. Trapped magma provides a physical, rather
than a chemical, mechanism for retaining volatiles in magma
oceans (Hier-Majumder and Hirschmann, 2017) and is highly
relevant for inhomogeneous crystallization paths in Earth- or
super-Earth-sized exoplanets (Moore and Cowan, 2020). The
amount of trapped liquid is also an expression of kinetic
processes and the competition of melt migration timescales
against crystallization timescales. Finally, recent work suggests
that large impacts may result in transient, highly energetic
periods in which the distinction between atmosphere and
surface may vanish (Caracas and Stewart, 2023). Upon cooling,
these atmospheres would shift from being silicate-rich to rich in
moderately volatile elements. Ultimately, all of these processes
must be accounted for to understand how much nature deviates
from the equilibrium framework. In light of associated degeneracy,
information from exoplanetary systems may provide additional
constraints on the redox diversity and crystallization pathways of
rocky planets within and beyond the Solar System.
4 Summary and outlook
The cores of rocky planets could host significant amounts of
volatile elements. However, a major finding from the recent
metal-silicate partitioning literature is that high pressures and
temperatures can have opposing effects on the partition
coefficients, and on average can lower the siderophile
tendencies of some elements including volatiles S and C. This
could result in decreased incorporation of these elements into Fe
cores during late-stage core formation in larger rocky planets.
Though partial equilibration of large impactors during the giant
impact phase of planetary growth could result in the transfer of
unequilibrated volatile-rich materials to cores. More
measurements at high P-T are needed to ascertain trends for
N and H. Both N and S appear to show increased affinity for iron
while C partitions less into the metal at more oxidizing
conditions. These change in siderophile behaviors of the
volatile elements has significant implications for the volatile
reservoirs as planets grow. When coupled with accretion
models, the metal-silicate partitioning measurements support
heterogeneous accretion scenarios whereby volatiles were
delivered towards the later stages of core formation. This is in
contrast with the increasing evidence for the volatile-rich nature
of inner Solar System planetesimals which could have strongly
influenced the volatile budgets of terrestrial planets. Though most
of the studies reviewed here were applied to the formation of the
Earth and other rocky Solar System bodies, it has been inferred
that core segregation likely occur during the formation of rocky
planets in extrasolar planetary systems and in planets larger than
the Earth such as super-earths and sub-neptunes (E.g., Otegi,
et al., 2020). Calculations have indicated efficient mixing between

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iron and rocky materials (Wahl and Militzer, 2015) and, similarly,
volatiles and rocky materials (Dorn and Lichtenberg, 2021;
Kovačević, et al., 2022; Vazan, et al., 2022) would occur in
such planets, and it would be beneficial to obtain
measurements at higher P-T and a wider range of
compositions than the current dataset to better understand
metal-rock and volatile-rock differentiation mechanisms in
super-Earths.
In the magma ocean stage of growth, significant amounts of
volatiles can dissolve into the silicate parts of planets, in which
solubilities and redox state determine the availability of volatiles to
outgassing. The recent solubility studies indicate that under oxidizing
conditions, most H and S are sequestered in the magma ocean, most
N is outgassed to the atmosphere, and C is nearly equally distributed
between the atmosphere and the interior. Under reducing conditions,
nearly all N dissolves in the magma ocean, the atmosphere becomes
the dominant C reservoir, H becomes more equally distributed
between the interior and the atmosphere, and S remains
dominantly in the interior. Coupling of measurements with
microphysical to large-scale models is a direction for future work
that could provide further clarity on some of these multi-scale
processes. Finally, the understanding gained from these studies can
guide the interpretation of new measurements of exoplanetary
atmospheres, which can in turn provide additional constraints to
assess the bulk compositions, formation histories, and the abilities of
rocky planets to develop conditions suitable for the origin and
sustainability of life as we know it.
Recent first principles/ab initio molecular dynamics and
density functional theory (DFT) simulations have been used to
gain further insights on how volatile elements are distributed
among cores, magmas, and atmospheres. For example
(Solomatova and Caracas, 2019; Davis, et al., 2022), found C
coordination in silicate melts to be largely pressure dependent,
implying that terrestrial magma oceans could have contained
oxidized carbon polymers. The latter study also found strong
clustering between C and Fe, which increases as a function of
pressure, suggesting C could be present in cores. Molecular
dynamics studies of Fe-N compounds lead to the conclusion
that Earth’s core likely contains very low amounts of nitrogen
(Bajgain, et al., 2019), though this does not rule out higher N
contents in the cores of other planets. DFT studies have been used
to argue for the preferential incorporation of H in the core (Li,
et al., 2020; Yuan and Steinle-Neumann, 2020). If validated by
meaurements, ab initio methods could provide a way to estimate
partition coefficients and solubilities at a wider range of
conditions than are achievable with current experiments. A
Bayesian inference approach might also provide a way to
extrapolate these quantities to conditions beyond the
measurements (e.g., Gaffney, et al., 2022).
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Author contributions
T-AS, CJ, DG, and CD contributed to the collection and curation
of the data. All authors contributed to the article and approved the
submitted version.
Acknowledgments
The results reported herein benefitted from collaborations and/or
information exchange within NASA’s Nexus for Exoplanet System
Science (NExSS) research coordination network sponsored by NASA’s
Science Mission Directorate and project “Alien Earths” funded under
Agreement No. 80NSSC21K0593. CRMJ acknowledges support from
NASA Emerging Worlds Grant 80NSSC21K0377. TL was supported
by the Branco Weiss Foundation. CD acknowledges ANR grant JCJC
CSI Planet. DG was funded by a Barr Foundation Postdoctoral
Fellowship by California Institute of Technology. This work was
supported by the AEThER project, funded by the Alfred P. Sloan
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work supported by the Center for Matter at Atomic Pressures
(CMAP), a National Science Foundation (NSF) Physics Frontiers
Center, under Award PHY2020249. The authors thank Vincent
Clesi for sharing data tables for hydrogen.
Conflict of interest
The authors declare that the research was conducted in the
absence of any commercial or financial relationships that could be
construed as a potential conflict of interest.
The handling editor MR declared a past collaboration with the
author CD.
Publisher’s note
All claims expressed in this article are solely those of the authors
and do not necessarily represent those of their affiliated organizations,
or those of the publisher, the editors and the reviewers. Any product
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manufacturer, is not guaranteed or endorsed by the publisher.
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